Formation of Passivate Interphases by Na<sub>3</sub>BS<sub>3</sub>-Glass Solid Electrolytes in All-Solid-State Sodium-Metal Batteries

Nasu, Akira; Inaoka, Takeaki; Tsuji, Fumika; Motohashi, Kota; Sakuda, Atsushi; Tatsumisago, Masahiro; Hayashi, Akitoshi

doi:10.1021/acsami.2c05090

Cited by 24 publications

(17 citation statements)

References 31 publications

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“…The corresponding Na metal symmetric cell exhibits short cycle life at relatively low current density and areal capacity (Figure S5). Na 3 B 5 S 9 is also not thermodynamically stable with Na metal, as B 3+ can be easily reduced to form Na−B alloy, as previously observed for Na 3 BS 3 glass [48] . The XPS of Na 3 B 5 S 9 powder mixed with Na metal (Figure S6) clearly shows the formation of Na 2 S and Na−B alloy.…”

Section: Resultsmentioning

confidence: 54%

A New Sodium Thioborate Fast Ion Conductor: Na₃B₅S₉

et al. 2023

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We report a new sodium fast-ion conductor, Na 3 B 5 S 9 , that exhibits a high Na ion total conductivity of 0.80 mS cm À 1 (sintered pellet; cold-pressed pellet = 0.21 mS cm À 1 ). The structure consists of corner-sharing B 10 S 20 supertetrahedral clusters, which create a framework that supports 3D Na ion diffusion channels. The Na ions are well-distributed in the channels and form a disordered sublattice spanning five Na crystallographic sites. The combination of structural elucidation via single crystal X-ray diffraction and powder synchrotron X-ray diffraction at variable temperatures, solid-state nuclear magnetic resonance spectra and ab initio molecular dynamics simulations reveal high Na-ion mobility (predicted conductivity: 0.96 mS cm À 1 ) and the nature of the 3D diffusion pathways. Notably, the Na ion sublattice orders at low temperatures, resulting in isolated Na polyhedra and thus much lower ionic conductivity. This highlights the importance of a disordered Na ion sublattice-and existence of well-connected Na ion migration pathways formed via face-sharing polyhedra -in dictating Na ion diffusion.

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Section: Resultsmentioning

confidence: 54%

A New Sodium Thioborate Fast Ion Conductor: Na₃B₅S₉

et al. 2023

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“…Na3BS3 has been reported to exhibit excellent reduction stability. 14 The cell exhibited initial sodiation and desodiation capacities of 616 and 228 mAh g -1 , respectively. The irreversible capacity during the initial cycle is 388 mAh g -1 .…”

Section: Resultsmentioning

confidence: 98%

“…Sulfide solid electrolytes of Na3BS3 glass (1.1×10 −5 S cm −1 ) and Na3PS4 glass-ceramics (2.0×10 −4 S cm −1 ) were prepared according to previous reports. [14][15][16] A 10 mm all-solid-state cell was fabricated using the following procedure. The working composite electrode (5 mg; 3 mg hard carbon)/Na3BS3 buffer layer (10 mg)/Na3PS4 separator layer (60 or 80 mg)/Na3BS3 buffer layer (10 mg)/Na15Sn4-KB composite 17 (50 mg) was stacked in that order.…”

Section: Preparation Of All-solid-state Cellsmentioning

confidence: 99%

“…Recently, we reported a Na3BS3 glass electrolyte with a high reduction stability and excellent formability. 14,15 A dense electrode layer is expected to be formed by cold pressing solely using Na3BS3 glass. All-solid-state cells using Na3BS3 glass electrolytes exhibit excellent reversibility of sodium plating and stripping.…”

Section: Introductionmentioning

confidence: 99%

“…All-solid-state cells using Na3BS3 glass electrolytes exhibit excellent reversibility of sodium plating and stripping. 14 Strictly, the Na3BS3 glass also reacts with sodium metal; however, the formation of a thin reaction interphase with an electronic insulating property suppresses reductive decomposition. 14 The formation of a passivate "interphase" by solid electrolyte decomposition contributes to the reversible operation of all-solid-state sodium batteries with hard carbon.…”

Section: Introductionmentioning

confidence: 99%

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Hard Carbon–Sulfide Solid Electrolyte Interface in All-Solid-State Sodium Batteries

YOSHIDA¹,

Nasu²,

Motohashi³

et al. 2023

Electrochemistry

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Hard carbon is a promising negative electrode material for sodium-ion batteries that operate at low potentials. However, reversible and high-capacity charging and discharging in all-solid-state sodium batteries with hard carbon electrodes using sulfide solid electrolytes have not been reported. This study reports that reductive decomposition of the sulfide solid electrolyte occurs at both the negative composite electrode and the interface between the negative electrode layer and the solid electrolyte layer. In the first cycle, the all-solid-state cell with a composite electrode containing a Na3PS4 solid electrolyte exhibited a large irreversible capacity of 561 mAh g −1 because of the reductive decomposition of Na3PS4 to Na2S and Na3P. The use of a Na3BS3 glass electrolyte with reduction stability can lead to the successful charging and discharging of all-solid-state cell that utilizes hard carbon. This glass electrolyte can serve as a solid electrolyte for the negative composite electrode and as a buffer layer between the negative electrode layer and the solid electrolyte layer. Hence, it can also help suppress the irreversible capacity of the cell to 122 mAh g −1 .

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Inorganic All‐Solid‐State Sodium Batteries: Electrolyte Designing and Interface Engineering

Yang,

Xue

et al. 2023

Advanced Materials

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Inorganic all‐solid‐state sodium batteries (IASSSBs) are emerged as promising candidates to replace commercial lithium‐ion batteries in large‐scale energy storage systems due to their potential advantages, such as abundant raw materials, robust safety, low price, high‐energy density, favorable reliability and stability. Inorganic sodium solid electrolytes (ISSEs) are an indispensable component of IASSSBs, gaining significant attention. Herein, this review begins by discussing the fundamentals of ISSEs, including their ionic conductivity, mechanical property, chemical and electrochemical stabilities. It then presents the crystal structures of advanced ISSEs (e.g., β/β′′‐alumina, NASICON, sulfides, complex hydride and halide electrolytes) and the related issues, along with corresponding modification strategies. The review also outlines effective approaches for forming intimate interfaces between ISSEs and working electrodes. Finally, current challenges and critical perspectives for the potential developments and possible directions to improve interfacial contacts for future practical applications of ISSEs are highlighted. This comprehensive review aims to advance the understanding and development of next‐generation rechargeable IASSSBs.This article is protected by copyright. All rights reserved

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Formation of Passivate Interphases by Na₃BS₃-Glass Solid Electrolytes in All-Solid-State Sodium-Metal Batteries

Cited by 24 publications

References 31 publications

A New Sodium Thioborate Fast Ion Conductor: Na₃B₅S₉

A New Sodium Thioborate Fast Ion Conductor: Na₃B₅S₉

Hard Carbon–Sulfide Solid Electrolyte Interface in All-Solid-State Sodium Batteries

Inorganic All‐Solid‐State Sodium Batteries: Electrolyte Designing and Interface Engineering

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Formation of Passivate Interphases by Na3BS3-Glass Solid Electrolytes in All-Solid-State Sodium-Metal Batteries

Cited by 24 publications

References 31 publications

A New Sodium Thioborate Fast Ion Conductor: Na3B5S9

A New Sodium Thioborate Fast Ion Conductor: Na3B5S9

Hard Carbon–Sulfide Solid Electrolyte Interface in All-Solid-State Sodium Batteries

Inorganic All‐Solid‐State Sodium Batteries: Electrolyte Designing and Interface Engineering

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Formation of Passivate Interphases by Na₃BS₃-Glass Solid Electrolytes in All-Solid-State Sodium-Metal Batteries

A New Sodium Thioborate Fast Ion Conductor: Na₃B₅S₉

A New Sodium Thioborate Fast Ion Conductor: Na₃B₅S₉